Process for carrying out washing operations with hard water



latter with aliphatic Patented Feb. 4,: 1930 UNITED STATES PATENT OFFICE eusrav ULLMANN, or VIENNA, AUSTRIA, AND WILL? sncx, or AUGSBU RG, GERMANY PROCESS FOR CARRYING- OU'I. WASHINGOPERA'IIONS WITH HARD WATER No Drawing. Application filed November 9, 1928,

The inventors have described a process for carrying out washing operations with hard water, which consists in rendering the hardening constituents and salts present in the washing water harmless by adding to the water as well as ordinary soap a soap indifferent to the substances which cause hardness in an are considerably more indiflerent to lime and other water-hardening substances than the aforementioned oil preparations. These new bodies are derivatives of organic aromatic sulphonic acids or condensation products of the V sulphonic acids, which on the one hand are distinguished by forming water-soluble salts with lime etc., and on the other hand, owing to their hi h molecular weight possess marked colloidal properties. I

' These sulphonic acids like the oil preparations indiflerent to lime mentioned above may be employed in amounts which are less than the quantities stoichiometrically equivalent to the substances which cause hardness in order to avoid the separation in soaping operations of lime soaps in the known sticky form and t0 efiect the separation of a finely-divided easily washable precipitate. This observed fact was all the more surprising as aromatic sulphonic acids of this kind in contradistinction to theloil preparations do not resemble true soaps ei her in their composition or in their propertles.

Examples of aromatic sul phonic acids of this kind which have'the action required for the process are in the first place the recently discovered aromatic or hydro-aromatic sulphonic acids with alkyl" side chains. The employment of products of this kind as wet-- Serial No. 318,305, aim in Austria August 5, 1927.

ting agents not however, their useuin soaping operations in less than stoichiometric quantities. Further, all compounds, which are obtained by the treatment of fatty oils with the above mentioned sulphonic acids, particularly the alkylated aromatic or hydro-aromatic sulphonic acids, either alone or in the presence of free sulphuric acid, belong to this group of bodies. These products also, which partially owing to their preponderating content of aromatic compounds are no longer to be considered as actual oil preparations, may be employed with equal success for the process according to this invention. Finally, the sulphonic acids contained in-the' decalcifiedsulphite waste liquor by conversion of the sulphurous acid ester fall in the group of the above mentioned compounds.

Example 1.Utility water having 18 German degrees of hardness (a German degree of hardness corresponding to one part of calcium oxide per 100,000 parts of water),with

and soap substitutes is known, I

which textile goods are to be washed, that is soaped and rinsed, is employed. A soap bath is prepared from 2 grams of soap containing 60% of fatty acid and 0.40 to 0.55 grams of isopropyl or di-isopropyl naphthalene sulphonic acid per litre.

Example 2.-The same procedure is followed as in Example 1. 'In place of isopropyl naphthalene sulphonic acid, a product, which. is obtained by the sulphonation of naphthalene or anthracene or phenanthrene iii the presence of other secondary or tertiaryialcohols which contain more than three carbon atoms, is employed in quantities corresponding to its lime-fixing power. In the same way, the hydrides ofthese bodies such as, for example, tetrahydronaphthalene isopropyl sulphonic acid may be employed.

Example 3.Water having 18 German deoperation. There -is added 0.65 grams of a product which is obtained by treating castor oil with one ofthe sulphonic acids mentioned in Example 1. The quantity 0.65 grams refers to a preparation which contains 30% of ricinoleic acid.

, colloidal properties,

Example 4.Water having 18 German degrees of hardness and 2.5 grams of soap per litre are used as in Example 1 for the soaping operation. In place of the preparation mentioned in Example 3, 0.65 grams of a 30% product which results from the treatment of castor oil with a mixture of concentrated sul phuric acid and one of the above mentioned aromatic sulphonic acids is employed.

Ewam-ple 5. -The soaping operation is effected as in Example 1. In place of one of the sulphonic acids mentioned, a sulphite waste liquor-in a quantity corresponding to its lime-fixing power% to of the quantity required for fixing the limeis employed. In this case 1.2 to 1.5 ccms. per litre of a preparation containing sulphite waste liquor having a dry content of 12% are necessary.

Ewample 6.The same procedure is followed as in Examples 1-5. Either 0.10 to 0.15 grams of urea or about 0.1 gram of neutral sodium lactate or a corresponding quantity of other stabilizers or peptizing agents is added as Well.

In the appended claims we intend the term aromatic to include the corresponding hydro-aromatic derivatives as well.

What we claim is I 1. In a process of launderingv in hard water the method of rendering harmless the substances contained in said water and which cause hardness thereof, consisting in adding to the water and ordinary soap a derivative of an aromatic sulphonic acid, which forms a water-soluble calcium salt and which has colloidal properties, in a proportion less than the quantity. chemically equivalent to said substances contained in the water.

2. In a process of laundering in hard water the method of rendering harmless the substances contained in said water and which cause hardness thereof, consisting in adding to the water and ordnary soap a compound comprising an aromatic sulphonic acid radi cal having an alkyl side chain, said compound forming a water-soluble calcium salt and having colloidal properties, in a proportion less than the quantity chemically equivalent to said substances contained in the water.

3., In a process of laundering inhard water the method of rendering harmlessthe substances contained in said water and which cause hardness thereof, consisting in adding to the water and ordinary soap a compound comprising a radical obtainable-by sulphonating a polynuclear aromatic hydrocarbon containing an'alkyl side chain with more than two carbon atoms, said compound forming a water-soluble; calcium salt and having in a proportion less than the quantity chemically equivalent to said substances contained inthe watenir In a process of launderingiii hard water the method of rendering harmless the suite the method of rendering harmless the sub-- stances contained in said water and which cause hardness thereof, conslsting in adding tothe water and ordinary soap a compound obtainable by sulphonating a polynuclear aromatic hydrocarbon containing. an alkyl side chain with more than two carbon atoms and then treating castor oil with the reaction product, said compound forming a watersoluble calcium salt and having colloidal properties, in a proportion less than the quantity chemically equivalent to said substances contained in the water.

- 6. In a process of laundering in hard water the method of rendering harmless the substances contained in said water and which cause hardness thereof, consisting in adding to the water and erdinary soap a compound obtainable by sulphonating a polynuclear aromatic hydrocarbon containing an alkyl side chain with more than two carbon atoms and then treating a fatty oil with the reaction product in the presence of concen-,

trated sulphuric acid, said compound form- 'ing a water-soluble calcium salt and having colloidal properties,in a proportion less than the quantity chemically equivalent to said substances contained in the water.

7. In a process of laundering in hard water the method of rendering harmless the substances contained in saidwater and which cause hardness thereof, consisting in adding to the water and ordinary soap a compound obtainable by sulphonating a polynuclear aromatic hydrocarbon containing an alkyl side chain with more than two carbonatoms and then treatingcastor oil with the reaction product in the presence of concentrated sulphuric acid, said compound forming a water-soluble calcium salt and having colloidal properties, in a proportion less than the quantity chemically equivalent to said substancescontained in the water.

In testimony whereof we fifiix our signatures.

GUSTAV ULLMANN. WILLY SECK. 

